CN114957782A - Boric acid composite type double-template magnetic molecularly imprinted polymer, preparation method and application - Google Patents
Boric acid composite type double-template magnetic molecularly imprinted polymer, preparation method and application Download PDFInfo
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- CN114957782A CN114957782A CN202210812495.2A CN202210812495A CN114957782A CN 114957782 A CN114957782 A CN 114957782A CN 202210812495 A CN202210812495 A CN 202210812495A CN 114957782 A CN114957782 A CN 114957782A
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- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 177
- 239000004327 boric acid Substances 0.000 title claims abstract description 119
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 96
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 59
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 54
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 41
- 239000005017 polysaccharide Substances 0.000 claims abstract description 41
- 239000004005 microsphere Substances 0.000 claims abstract description 40
- 239000011258 core-shell material Substances 0.000 claims abstract description 33
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 32
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229960003638 dopamine Drugs 0.000 claims abstract description 16
- 239000007853 buffer solution Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 150000004676 glycans Chemical class 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 235000019441 ethanol Nutrition 0.000 claims description 49
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 44
- 239000003463 adsorbent Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 239000010954 inorganic particle Substances 0.000 claims description 27
- 239000006249 magnetic particle Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003980 solgel method Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001566 austenite Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- KFVJSOMXADHNEH-UHFFFAOYSA-N 2-methylprop-2-enoic acid 1,1,1-trimethoxypropane Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(OC)(OC)OC KFVJSOMXADHNEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 93
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- -1 boric acid compound Chemical class 0.000 description 49
- 150000004804 polysaccharides Chemical class 0.000 description 37
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 29
- 229940098773 bovine serum albumin Drugs 0.000 description 29
- 230000010355 oscillation Effects 0.000 description 27
- 229920001503 Glucan Polymers 0.000 description 25
- 238000007885 magnetic separation Methods 0.000 description 24
- 239000012528 membrane Substances 0.000 description 16
- 229920002307 Dextran Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 102000016943 Muramidase Human genes 0.000 description 6
- 108010014251 Muramidase Proteins 0.000 description 6
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 239000004325 lysozyme Substances 0.000 description 6
- 229960000274 lysozyme Drugs 0.000 description 6
- 235000010335 lysozyme Nutrition 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000855 Fucoidan Polymers 0.000 description 1
- 102000007982 Phosphoproteins Human genes 0.000 description 1
- 108010089430 Phosphoproteins Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 230000005496 eutectics Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000004503 metal oxide affinity chromatography Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000013586 microbial product Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/76—Albumins
- C07K14/765—Serum albumin, e.g. HSA
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The invention provides a boric acid composite type double-template magnetic molecularly imprinted polymer, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1 preparation of Fe 3 O 4 @SiO 2 The microsphere material: s2 for Fe 3 O 4 @SiO 2 Carrying out double bond modification on the microsphere material; s3, modifying double bond into epoxy bond to obtain Fe 3 O 4 @SiO 2 -EPO; s4, grafting a combined borate on the epoxy bond; s5, fully dissolving the combined borate affinity core-shell structure magnetic nanoparticles and the double-template molecules in a buffer solution, adding dopamine and an initiator, and polymerizing to obtain the boric acid composite double-template magnetic molecularly imprinted polymer. The preparation method is simple, raw materials are easy to obtain, the solid-liquid separation speed is high, the energy consumption is low, the prepared magnetic molecularly imprinted polymer is stable in adsorption performance, easy to separate and reusable for multiple times, and two template molecules of protein and polysaccharide substances can be adsorbed simultaneously.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a boric acid composite type double-template magnetic molecularly imprinted polymer, a preparation method and application thereof.
Background
In recent years, Membrane Bioreactor (MBR) technology has attracted attention because of its many advantages different from the conventional technology, however, the membrane flux is reduced, membrane cleaning and replacement are difficult, and operation cost is increased due to membrane pollution, which severely limits the large-scale popularization and application of MBR. Soluble microorganism products are considered to be the main cause of membrane pollution, and soluble microorganisms mainly comprise protein, polysaccharide and other biological macromolecules, so that the research on preparing materials for specifically adsorbing the biological macromolecules (such as protein and polysaccharide) polluted by the membrane can obviously improve the effective adsorption efficiency, delay the material replacement period and reduce the operation cost. The Molecularly Imprinted Polymers (MIPs) synthesized by adopting the Molecular Imprinting Technology (MIT) can realize selective adsorption of target molecules, compared with other separation materials, the MIPs have the advantages of high selective identification, strong designability, simplicity and convenience in preparation and the like, and have wide application prospects in multiple fields of material separation and purification, biomimetic sensing, drug analysis, environmental management and the like.
The traditional MIPs are limited in development and application due to the problems of complex solid-liquid separation, difficult recovery and the like, and the magnetic material has the characteristics of easiness in recovery and separation, superparamagnetism and the like.
As the research advances, the imprinting technology for biomacromolecules has been developed, in which the boric acid affinity method enhances the specificity to carbohydrate biomacromolecules, while the dopamine autopolymerization method using dopamine as a functional monomer improves the imprinting efficiency of molecular imprinting on protein types, for example (Fan X W, Wang Z D, Sun N R, et al. magnetic metal oxide affinity chromatography used for imprinting on protein type)]Talanta, 2021, 226: 122143) with Fe 3 O 4 @TiO 2 As a carrier, the phosphoprotein lysozyme is used as a template molecule, the polydopamine is used as a polymer layer to prepare the magnetic molecularly imprinted nano-particle, the magnetic molecularly imprinted material shows extremely low detection limit in a standard solution, separation in human serum and urine shows expected excellent performance, and the magnetic molecularly imprinted material shows great potential in the aspects of separating and purifying protein biomarkers.
The conventional magnetic molecular imprinting material of single-mode plate can usually achieve very high selective adsorption effect on a substance, and the acrylamide is reported as a functional monomer and the lysozyme is imprinted on the surface of activated silica in the literature (ZHao W T, Xue B, Chen Z H. Nano-silica particles enhanced adsorption and recognition of lysozyme on imprinted polymers [ J ]. Journal of Beijing Institute of Technology,2015,24 (4)), and the adsorption result shows that the adsorption capacity of the obtained polymer on lysozyme is 56mg/g, and the obtained polymer shows better selectivity on lysozyme in a binary adsorption system of Bovine Serum Albumin (BSA) and lysozyme. But aiming at the soluble microbial products which cause the membrane pollutants, one magnetic molecular imprinting material can only adsorb one type of membrane pollutants, while the dual-template molecular imprinting can improve the adsorption efficiency of the molecularly imprinted material, the document (Li G Z, Row K H. magnetic molecular imprinted polymers for registration and evaluation of polysaccharides from seawell [ J ]. Journal of Separation Science, 2017, 40 (24): 4765) 4772) prepares a dual-template magnetic molecularly imprinted material by taking alginate and alginic acid as templates, the material is modified by 7 types of deep eutectic solvents, and the results show that the actual recovery rates of fucoidan and alginic acid of the modified magnetic molecularly imprinted material are 89.87% and 92.0% respectively, the actual extraction amounts are 20.6 mu g-1 and 18.7 mu g-1 respectively, and the modified magnetic molecularly imprinted material shows excellent separation and purification effects.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the boric acid composite type dual-template magnetic molecularly imprinted polymer which is simple to prepare, stable in adsorption performance, easy to separate and capable of being repeatedly used, the preparation method and the application, and the magnetic molecularly imprinted polymer can be used for selectively separating and enriching protein and polysaccharide biomacromolecules in a complex system and can also be used for adsorbing and removing protein and polysaccharide substances in domestic sewage and industrial wastewater.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a boronic acid composite type dual-template magnetic molecularly imprinted polymer, the method comprising the steps of:
s1 preparation of Fe by sol-gel method 3 O 4 @SiO 2 The microsphere material:
s2, dispersing 3- (methacryloyloxy) propyltrimethoxysilane in a mixed solution of acid and water, and then adding Fe 3 O 4 @SiO 2 Reacting the microsphere material in a water bath at 30-60 ℃ to obtain double bond modified Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles;
s3, mixing the Fe 3 O 4 @SiO 2 Modifying double bonds on the surface of the @ C ═ C magnetic particles into epoxy bonds to obtain the epoxy bond modified magnetic nanoparticles Fe with the core-shell structure 3 O 4 @SiO 2 -EPO；
S4, in the presence of Fe 3 O 4 @SiO 2 Grafting a combined borate on the epoxy bond of EPO to obtain a combined borate affinity core-shell knotMagnetic nanoparticles as magnetic carriers;
s5, weighing and fully dissolving the combined borate affinity core-shell structure magnetic nanoparticles and the double-template molecules in a buffer solution, oscillating for 1-5 h at room temperature, then adding dopamine and an initiator, and carrying out polymerization reaction for 2-8 h to obtain the boric acid composite double-template magnetic molecularly imprinted polymer.
Preferably, the sol-gel method described in step S1 prepares Fe 3 O 4 @SiO 2 The method for preparing the microsphere material specifically comprises the following steps:
s11, dispersing magnetic inorganic particles in a mixed solution of alcohol and water, adding an alkaline solution under the stirring condition, then adding an ethyl orthosilicate solution, and reacting at room temperature for 6-12 hours to obtain a coating;
s12, alternately washing the coating in the step S11 with absolute ethyl alcohol and distilled water for a plurality of times, then carrying out solid-liquid separation, drying the solid obtained by separation in a vacuum drying oven at 50-70 ℃ for 8-24 h to obtain SiO 2 5 to 25 weight percent of Fe 3 O 4 @SiO 2 A microsphere material.
Preferably, the magnetic inorganic particles in step S11 are Fe 3 O 4 Or gamma-Fe 2 O 3 The size of the magnetic inorganic particles is 20 nm-30 mu m.
Preferably, the first alcohol solution in step S11 includes a first alcohol and water, and the first alcohol is one or a combination of methanol, ethanol, propanol and butanol; the second glycol solution of the ethyl orthosilicate is formed by adding the ethyl orthosilicate into the second glycol solution for dilution, wherein the second glycol solution is one or a combination of methanol, ethanol, propanol and butanol; the volume ratio of the ethyl orthosilicate to the second alcohol solution is 1: 2-1: 10, the volume ratio of the ethyl orthosilicate to the first alcohol is 1: 10-1: 50, and the volume ratio of the ethyl orthosilicate to the water is 1: 1-1: 15.
Preferably, the ratio of the mass of the magnetic inorganic particles to the volume of the tetraethoxysilane in step S11 is 1:0.5 to 1:15, and the volume ratio of the tetraethoxysilane to the alkaline solution is 1:0.5 to 1: 10.
Preferably, the Fe is followed in step S11 3 O 4 @SiO 2 The mass percentage of the microsphere material is that Fe 3 O 4 @SiO 2 The microsphere material comprises 0.2-12 wt% of magnetic inorganic particles, 0.3-15 wt% of ethyl orthosilicate, 2-10 wt% of alkaline solution and the balance of mixed solution of alcohol and water.
Preferably, the Fe added in step S2 3 O 4 @SiO 2 The ratio of the mass of the microsphere material to the volume of the 3- (methacryloyloxy) propyltrimethoxysilane is 1: 0.1-1: 5.
Preferably, the volume ratio of the 3- (methacryloyloxy) propyltrimethoxysilane to the acid in the step S2 is 1: 5-1: 25.
Preferably, the acid in step S2 is one or a combination of acetic acid, phosphoric acid, and sulfuric acid.
Preferably, the Fe is added in step S3 3 O 4 @SiO 2 The double bond modification on the surface of the @ C ═ C magnetic particle is an epoxy bond, and specifically includes: subjecting said Fe to 3 O 4 @SiO 2 Dispersing the @ C ═ C magnetic particles in acetonitrile solution, adding glycidyl methacrylate, a crosslinking agent and azodiisobutyronitrile, and reacting in a water bath at 85-95 ℃ to obtain epoxy bond modified core-shell structure magnetic nanoparticles Fe 3 O 4 @SiO 2 -EPO。
Preferably, the glycidyl methacrylate and the Fe in step S3 3 O 4 @SiO 2 The mass ratio of @ C ═ C magnetic particles is 1:1 to 1: 5.
Preferably, the cross-linking agent is reacted with the Fe in step S3 3 O 4 @SiO 2 The mass ratio of @ C ═ C magnetic particles is 1:1 to 1: 5.
Preferably, the mass ratio of the azobisisobutyronitrile to the glycidyl methacrylate in the step S3 is 1:20 to 1: 50.
Preferably, the cross-linking agent in step S3 is one or a combination of N, N-methylene bisacrylamide, N-1, 2-dihydroxyethylene bisacrylamide, vinyl dimethacrylate, and trimethoxypropane trimethacrylate.
Preferably, in step S4, the Fe is 3 O 4 @SiO 2 -grafted on the epoxy bond of EPO a combined borate, comprising in particular: adding 3-aminophenylboronic acid and 1, 6-hexamethylenediamine into a container filled with absolute ethyl alcohol, stirring for 30-90 min, and then adding the Fe 3 O 4 @SiO 2 Continuously reacting for 12 hours at the temperature of 80 ℃ in a water bath, washing the obtained product with absolute ethyl alcohol for several times, then carrying out solid-liquid separation, and drying the separated solid to obtain the combined borate affinity core-shell structure magnetic nanoparticles;
wherein the 3-aminophenylboronic acid is reacted with the Fe 3 O 4 @SiO 2 The mass ratio of EPO is 1: 0.2-1: 2; the 1, 6-hexanediamine and the Fe 3 O 4 @SiO 2 The mass ratio of EPO to EPO is 1: 0.2-1: 2.
Preferably, in step S5, the dual-template molecules include proteins and polysaccharides, and the mass ratio of the proteins to the polysaccharides is 1: 1-1: 5.
Preferably, in step S5, the mass ratio of the dual-template molecules to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 10-1: 30, the mass ratio of dopamine to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 1-1: 5, and the volume ratio of the initiator to the buffer solution is 1: 10-1: 30, wherein the initiator is ammonium persulfate, and the buffer solution is a phosphate buffer solution.
The invention also provides a boric acid composite type double-template magnetic molecularly imprinted polymer which is prepared by adopting the preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer.
The invention also provides application of the boric acid composite type double-template magnetic molecularly imprinted polymer, and the boric acid composite type double-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein and polysaccharide substances.
As mentioned above, the boric acid compound type double-template magnetic molecularly imprinted polymer, the preparation method and the application have the following beneficial effects:
the invention uses magnetic inorganic particles Fe 3 O 4 Or gamma-Fe 2 O 3 As a core, Fe is formed by coating silica on the surface thereof by a sol-gel method 3 O 4 @SiO 2 Microsphere material of Fe 3 O 4 @SiO 2 The microsphere material has the advantages of low cost of raw materials, simple preparation, good water solubility, dispersibility and biocompatibility, and the surface can be modified with different functional groups through chemical modification, and the Fe is firstly modified by 3- (methacryloyloxy) propyl trimethoxy silane 3 O 4 @SiO 2 Carrying out double bond modification on the microsphere material, and modifying epoxy bonds at the double bonds by using the double bonds to obtain the epoxy bond modified magnetic nanoparticles with the core-shell structure Fe 3 O 4 @SiO 2 EPO, synthesizing a boric acid composite type double-template molecularly imprinted polymer by a boric acid affinity imprinting method and a dopamine autopolymerization imprinting technology, and specifically binding polysaccharides and proteins at the same time; in addition, the invention utilizes the characteristics of the magnetic material, adopts the magnet to separate solid from liquid, has high solid-liquid separation speed and low energy consumption, and has the advantages of easily obtained raw materials, simple and quick method, easy separation and recycling.
The boric acid compound type double-template molecularly imprinted polymer prepared by the invention is used as a magnetic imprinted adsorbent, has high adsorption rate and stable adsorption performance, is easy to separate and can be repeatedly used for many times, can simultaneously adsorb two template molecules of protein and polysaccharide substances, is not only suitable for selectively removing membrane pollutants such as protein, polysaccharide and the like in an adsorption membrane biological reaction system, but also is suitable for separating, purifying and enriching protein, polysaccharide and other types of biomacromolecules in other fields.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention uses magnetic inorganic particles Fe 3 O 4 Or gamma-Fe 2 O 3 As a core, Fe is formed by coating silica on the surface thereof by a sol-gel method 3 O 4 @SiO 2 Microsphere material of Fe 3 O 4 @SiO 2 The microsphere material has the advantages of low cost of raw materials, simple preparation, good water solubility, dispersibility and biocompatibility, and the surface can be modified with different functional groups through chemical modification, and the Fe is firstly modified by 3- (methacryloyloxy) propyl trimethoxy silane 3 O 4 @SiO 2 Carrying out double bond modification on the microsphere material, and modifying an epoxy bond at the double bond by using the double bond to obtain the epoxy bond modified magnetic nano particle Fe with the core-shell structure 3 O 4 @SiO 2 EPO, synthesizing a boric acid composite type double-template molecularly imprinted polymer by a boric acid affinity imprinting method and a dopamine autopolymerization imprinting technology, and specifically binding polysaccharides and proteins at the same time; in addition, the invention utilizes the characteristics of magnetic materials, adopts the magnet to separate solid from liquid, has high solid-liquid separation speed and low energy consumption, and has the advantages of easily obtained raw materials, simple and rapid method, easy separation and recycling; the boric acid compound type double-template molecularly imprinted polymer prepared by the invention is used as a magnetic imprinted adsorbent, has high adsorption rate and stable adsorption performance, is easy to separate and can be repeatedly used for many times, can simultaneously adsorb two template molecules of protein and polysaccharide substances, is not only suitable for selectively removing membrane pollutants such as protein, polysaccharide and the like in an adsorption membrane biological reaction system, but also is suitable for separating, purifying and enriching protein, polysaccharide and other types of biomacromolecules in other fields.
The invention provides a preparation method of a boric acid composite type double-template magnetic molecularly imprinted polymer, which comprises the following steps:
s1 preparation of Fe by sol-gel method 3 O 4 @SiO 2 The microsphere material:
s2 preparation of 3- (methacryloyloxy) propyl triDispersing methoxysilane in mixed solution of acid and water, and adding Fe 3 O 4 @SiO 2 Reacting the microsphere material in a water bath at 30-60 ℃ to obtain double bond modified Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles;
s3, mixing Fe 3 O 4 @SiO 2 Modifying double bonds on the surface of the @ C ═ C magnetic particles into epoxy bonds to obtain the epoxy bond modified magnetic nanoparticles Fe with the core-shell structure 3 O 4 @SiO 2 -EPO；
S4 at Fe 3 O 4 @SiO 2 Grafting a combined borate on an epoxy bond of EPO to obtain a combined borate affinity core-shell structure magnetic nanoparticle which is used as a magnetic carrier;
s5, weighing and fully dissolving the combined borate affinity core-shell structure magnetic nanoparticles and the double-template molecules in a buffer solution, oscillating for 1-5 h at room temperature, then adding dopamine and an initiator, and carrying out polymerization reaction for 2-8 h to obtain the boric acid composite double-template magnetic molecularly imprinted polymer.
In particular, with Fe 3 O 4 @SiO 2 The microsphere material is used as a substrate, the surface of the microsphere material is functionally modified, firstly, a modified double bond is introduced, then, the double bond is modified into an epoxy bond, after the functional modification, a combined borate strategy is applied to the modified double bond, the obtained combined borate affinity core-shell structure magnetic nanoparticles are used as a magnetic carrier, and then, according to dopamine self-polymerization reaction, a double-template molecule is imprinted on the surface of the imprinted adsorption material which is used as a template.
The water bath temperature in the step S2 may include values in any range of 30 ℃, 40 ℃, 50 ℃, 60 ℃ and the like, and is specifically adjusted according to the actual conditions; washing the product obtained after the reaction under the water bath condition for several times without over limitation, separating the product with a magnet to obtain a solid product, and drying the solid product in vacuum to obtain the double-bond modified Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles.
The time of oscillation at room temperature in step S5 may include values within any range, such as 1h, 2h, 3h, 4h, 5h, and the like, and is specifically adjusted according to the actual conditions; the time of the polymerization reaction can comprise values in any range of 2h, 4h, 6h, 8h and the like, and is specifically adjusted according to the actual conditions; after the polymerization reaction, the obtained product needs to be washed with absolute ethyl alcohol and distilled water for several times, then washed with eluent for several times to remove double-template molecules, washed with distilled water to be neutral, and finally dried to obtain the boric acid composite double-template magnetic molecularly imprinted polymer; wherein the eluent is a mixed solution of 5 wt% of sodium dodecyl sulfate and 5 wt% of acetic acid, and the pH value is 3.0-6.0.
As an example, the sol-gel method of step S1 prepares Fe 3 O 4 @SiO 2 The method for preparing the microsphere material specifically comprises the following steps:
s11, dispersing magnetic inorganic particles in a mixed solution of alcohol and water, adding an alkaline solution under the stirring condition, then adding an ethyl orthosilicate solution, and reacting at room temperature for 6-12 hours to obtain a coating; wherein the ethyl orthosilicate solution is an alcoholic solution of ethyl orthosilicate, that is, the ethyl orthosilicate is dissolved in alcohol, and the alcohol can be one or a combination of methanol, ethanol, propanol and butanol; and the water is a reactant for hydrolyzing the tetraethoxysilane, the alkaline solution is a catalyst in the reaction process, and the concentration and the flow rate of the mixed solution of the alcohol and the water enable the tetraethoxysilane to form gelation on the surfaces of the magnetic inorganic particles in the solution.
S12, washing the coated object in the step S11 with absolute ethyl alcohol and distilled water alternately for a plurality of times, then carrying out solid-liquid separation, drying the separated solid in a vacuum drying oven at 50-70 ℃ for 8-24 h to obtain SiO 2 5 wt% -25 wt% of Fe 3 O 4 @SiO 2 A microsphere material.
Specifically, before dispersing the magnetic inorganic particles in the mixed solution of alcohol and water in step S11, pretreatment of the magnetic inorganic particles is required, and the pretreatment specifically includes: the magnetic inorganic particles are soaked in hydrochloric acid solution to activate the surface hydroxyl groups of the magnetic inorganic particles, and then washed with distilled water under the condition of an external magnetic field to remove hydrochloric acid interference.
In addition, the reaction time at room temperature in step S11 may include 6h, 8h, 10h, 12hAnd the like in any range, and are specifically adjusted according to the actual conditions; the number of times of alternately washing the coating with absolute ethyl alcohol and distilled water in step S12 may be 2, 3, 4, etc., and the specific number of times of washing is not excessively limited herein; the solid-liquid separation is performed by adopting magnet separation, the solid obtained by separation is placed in a vacuum drying oven for drying, the specific drying temperature can include values in any range of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and the like, and the specific drying temperature is adjusted according to the actual conditions; the drying time can comprise values in any range of 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h and the like, and is specifically adjusted according to the actual conditions; obtained Fe 3 O 4 @SiO 2 SiO in microsphere material 2 The mass percentage of (b) may include any range of values of 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, etc., as the case may be.
As an example, the magnetic inorganic particles in step S11 are Fe 3 O 4 Or gamma-Fe 2 O 3 The size of the magnetic inorganic particles is 20 nm-30 μm.
Specifically, the size of the magnetic inorganic particles may include values in any range of 20nm, 500nm, 1 μm, 5 μm, 15 μm, 25 μm, 30 μm, and the like, which are adjusted in particular according to the actual circumstances;
the first alcohol solution in the step S11 includes a first alcohol and water, the first alcohol is one or a combination of methanol, ethanol, propanol and butanol; the second glycol solution of the ethyl orthosilicate is formed by adding the ethyl orthosilicate into the second glycol solution for dilution, wherein the second glycol solution is one or a combination of methanol, ethanol, propanol and butanol; the volume ratio of the ethyl orthosilicate to the second alcohol solution is 1: 2-1: 10, the volume ratio of the ethyl orthosilicate to the first alcohol is 1: 10-1: 50, and the volume ratio of the ethyl orthosilicate to the water is 1: 1-1: 15.
Specifically, the volume ratio of the tetraethoxysilane to the second glycol solution can include any range of values such as 1:2, 1:5, 1:10 and the like, and is specifically adjusted according to the actual conditions; the volume ratio of the ethyl orthosilicate to the first alcohol in the first alcohol solution can include any range of values such as 1:10, 1:20, 1:30, 1:40, 1:50 and the like, and is adjusted according to actual conditions; the volume ratio of the ethyl orthosilicate to the water in the first alcohol solution can include any range of values such as 1:1, 1:5, 1:10, 1:15 and the like, and is adjusted according to actual conditions; the first alcohol and the second alcohol solution in the first alcohol solution may be the same alcohol or different alcohols, and preferably, the first alcohol and the second alcohol solution used in the first alcohol solution are the same alcohol in the same solution system.
Preferably, the volume ratio of the ethyl orthosilicate to the second alcohol solution is 1:2 to 1:5 (e.g., 1:2, 1:3, 1:4), the volume ratio of the ethyl orthosilicate to the first alcohol is 1:20 to 1:40 (e.g., 1:20, 1:30, 1:40), and the volume ratio of the ethyl orthosilicate to the water is 1:1 to 1:10 (e.g., 1:1, 1:3, 1:5, 1:7, 1:9, 1:10, etc.).
For example, in step S11, the ratio of the mass of the magnetic inorganic particles to the volume of the tetraethoxysilane is 1:0.5 to 1:15, and the volume ratio of the tetraethoxysilane to the alkaline solution is 1:0.5 to 1: 10.
Specifically, the ratio of the mass of the magnetic inorganic particles to the volume of the tetraethoxysilane may include values in any range of 1:0.5, 1:1, 1:5, 1:10, 1:15, and the like, which are specifically adjusted according to the actual conditions; the volume ratio of the ethyl orthosilicate to the alkaline solution can include any range of values such as 1:0.5, 1:1, 1:5, 1:10 and the like, and is specifically adjusted according to the actual conditions; wherein, in this embodiment, the alkaline solution is NH 3 ·H 2 O。
Preferably, the ratio of the mass of the magnetic inorganic particles to the volume of the tetraethoxysilane is 1:1 to 1:5 (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, etc.); the volume ratio of the ethyl orthosilicate to the alkaline solution is 1: 1-1: 10 (for example, 1:1, 1:3, 1:5, 1:7, 1:9, 1:10, etc.).
As an example, in terms of Fe 3 O 4 @SiO 2 Mass percent of the microsphere material, Fe 3 O 4 @SiO 2 The microsphere material comprises 0.2-12 wt% of magnetic inorganic particles, 0.3-15 wt% of ethyl orthosilicate, 2-10 wt% of alkaline solution and the balance of mixed solution of alcohol and water.
Specifically, the magnetic inorganic particles may include values in any range of 0.2 wt%, 1 wt%, 2 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, etc., which are adjusted in particular according to the actual circumstances; the ethyl orthosilicate can comprise any range of values, such as 0.3 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, etc., specifically adjusted according to the actual application; the alkaline solution may include values in any range of 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, etc., which are adjusted according to the actual circumstances.
As an example, Fe added in step S2 3 O 4 @SiO 2 The ratio of the mass of the microsphere material to the volume of the 3- (methacryloyloxy) propyltrimethoxysilane is 1: 0.1-1: 5.
In particular, Fe 3 O 4 @SiO 2 The ratio of the mass of the microsphere material to the volume of the 3- (methacryloyloxy) propyltrimethoxysilane can include any range of values such as 1:0.1, 1:0.5, 1:1, 1:3, 1:5, and the like, and is adjusted according to the actual application.
In step S2, the volume ratio of 3- (methacryloyloxy) propyltrimethoxysilane to the acid is 1: 5-1: 25.
Specifically, the volume ratio of 3- (methacryloyloxy) propyltrimethoxysilane to the acid may include any range of values such as 1:5, 1:10, 1:15, 1:20, 1:25, etc., and is adjusted according to the actual application.
In step S2, the acid is one or a combination of acetic acid, phosphoric acid and sulfuric acid.
Preferably, Fe is added in step S2 3 O 4 @SiO 2 The ratio of the mass of the microsphere material to the volume of the 3- (methacryloyloxy) propyltrimethoxysilane is 1: 0.5-1: 2 (such as 1:0.5, 1:1, 1:1.5, 1:2, etc.); the volume ratio of the 3- (methacryloyloxy) propyltrimethoxysilane to the acid is 1: 5-1: 15 (such as 1:5, 1:8, 1:10, 1:12, 1:15, etc.).
As an example, Fe is added in step S3 3 O 4 @SiO 2 The double bond modification on the surface of the @ C ═ C magnetic particle is an epoxy bond, and specifically includes: mixing Fe 3 O 4 @SiO 2 Dispersing the @ C ═ C magnetic particles in acetonitrile solution, adding glycidyl methacrylate, a crosslinking agent and azodiisobutyronitrile, and reacting in a water bath at 85-95 ℃ to obtain epoxy bond modified core-shell structure magnetic nanoparticles Fe 3 O 4 @SiO 2 -EPO。
Specifically, the temperature of the water bath can include any value in the range of 85 ℃, 87 ℃, 89 ℃, 90 ℃, 91 ℃, 93 ℃, 95 ℃ and the like, and is adjusted according to the actual conditions; in the reaction process under the condition of water bath at 85-95 ℃, condensing and collecting acetonitrile solution, boiling the acetonitrile solution at 81.6 ℃, condensing and collecting, boiling, condensing and collecting the acetonitrile solution for 30-180 min, stopping heating, washing with absolute ethyl alcohol for several times (the specific times are not limited excessively), performing solid-liquid separation by using a magnet to obtain magnetic solid, and drying to obtain the epoxy bond modified magnetic nano particle Fe with the core-shell structure 3 O 4 @SiO 2 -EPO; the volume ratio of the liquid collected by condensing the acetonitrile to the added acetonitrile is 1: 2-1: 5, and specifically can include values in any range of 1:2, 1:3, 1:4, 1:5 and the like, and is specifically adjusted according to the actual conditions.
As an example, glycidyl methacrylate and Fe in step S3 3 O 4 @SiO 2 The mass ratio of the @ C ═ C magnetic particles is 1:1 to 1: 5.
In particular, glycidyl methacrylate and Fe 3 O 4 @SiO 2 The mass ratio of @ C ═ C magnetic particles may include values in any range of 1:1, 1:2, 1:3, 1:4, 1:5, and the like, specifically adjusted according to the actual.
Step S3 Cross-linker with Fe 3 O 4 @SiO 2 The mass ratio of the @ C ═ C magnetic particles is 1:1 to 1: 5.
In particular, a crosslinking agent with Fe 3 O 4 @SiO 2 The mass ratio of @ C ═ C magnetic particles may include values in any range of 1:1, 1:2, 1:3, 1:4, 1:5, and the like, specifically adjusted according to the actual.
In the step S3, the mass ratio of the azobisisobutyronitrile to the glycidyl methacrylate is 1: 20-1: 50.
Specifically, the mass ratio of azobisisobutyronitrile to glycidyl methacrylate may include any range of values such as 1:20, 1:30, 1:40, 1:50, etc., which is adjusted according to the actual application.
In step S3, the cross-linking agent is one or a combination of N, N-methylene bisacrylamide, N-1, 2-dihydroxyethylene bisacrylamide, vinyl dimethacrylate and trimethoxypropane trimethacrylate.
As an example, in step S4 Fe 3 O 4 @SiO 2 -grafted on the epoxy bond of EPO a combined borate, comprising in particular: adding 3-aminophenylboronic acid and 1, 6-hexamethylenediamine into a container filled with absolute ethyl alcohol, stirring for 30-90 min, and then adding Fe 3 O 4 @SiO 2 Continuously reacting for 12 hours at the temperature of 80 ℃ in a water bath, washing the obtained product for several times by using absolute ethyl alcohol, then carrying out solid-liquid separation, and drying the separated solid to obtain the combined borate affinity core-shell structure magnetic nanoparticles;
wherein, the 3-aminophenylboronic acid is reacted with Fe 3 O 4 @SiO 2 The mass ratio of EPO is 1: 0.2-1: 2; 1, 6-hexanediamine with Fe 3 O 4 @SiO 2 The mass ratio of EPO to EPO is 1: 0.2-1: 2.
Specifically, the 3-aminophenylboronic acid and the 1, 6-hexamethylenediamine are added into a container filled with the absolute ethyl alcohol and stirred for any value within any range of 30min, 40min, 50min, 60min, 70min, 80min, 90min and the like, and the stirring time is specifically adjusted according to the actual condition; 3-Aminophenylboronic acid with Fe 3 O 4 @SiO 2 The EPO mass ratio may comprise values in any range of 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, etc., adjusted in particular to the actual case; 1, 6-hexanediamine with Fe 3 O 4 @SiO 2 The mass ratio of-EPO may include values in any range of 0.2, 1:0.5, 1:1, 1:1.5, 1:2, etc., which are adjusted according to the actual circumstances.
Illustratively, the dual-template molecules in the step S5 comprise protein and polysaccharide substances, wherein the mass ratio of the protein to the polysaccharide substances is 1: 1-1: 5;
in the step S5, the mass ratio of the double-template molecules to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 10-1: 30, the mass ratio of the dopamine to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 1-1: 5, and the volume ratio of the initiator to the buffer solution is 1: 10-1: 30, wherein the initiator is ammonium persulfate, and the buffer solution is phosphate buffer solution.
Specifically, the mass ratio of the double-template molecules to the combined borate affinity core-shell structure magnetic nanoparticles can include values in any range of 1:10, 1:15, 1:20, 1:25, 1:30 and the like, and is specifically adjusted according to the actual conditions; the mass ratio of the dopamine to the combined borate affinity core-shell structure magnetic nanoparticles can be adjusted according to actual conditions, wherein the mass ratio of the dopamine to the combined borate affinity core-shell structure magnetic nanoparticles can be any value within the range of 1:1, 1:2, 1:3, 1:4, 1:5 and the like; the volume ratio of the initiator to the buffer solution may include any value within any range of 1:10, 1:15, 1:20, 1:25, 1:30, etc., and is adjusted according to the actual situation.
The invention also provides a boric acid composite type double-template magnetic molecularly imprinted polymer which is prepared by adopting the preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer.
In order to better understand the boric acid compound type double-template magnetic molecularly imprinted polymer, the invention also provides application of the boric acid compound type double-template magnetic molecularly imprinted polymer, and the boric acid compound type double-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein and polysaccharide substances.
Specifically, the boric acid composite type double-template magnetic molecularly imprinted polymer is used as an adsorbent and is dispersed in an operating MBR system (membrane biological reaction system) for adsorption reaction, the addition of the magnetic molecularly imprinted polymer can generate a magnetobiological effect, the characteristics of a mixture can be effectively regulated and controlled, and the adsorbent is subjected to solid-liquid separation through an external magnetic field to obtain the magnetic molecularly imprinted polymer adsorbed with protein and polysaccharide macromolecules.
The desorption and activation method for the magnetic protein molecular engram polymer absorbed with protein comprises the following steps: and (2) placing the magnetic protein molecularly imprinted polymer adsorbed with the protein into a phosphoric acid buffer solution containing 5% by volume of acetic acid and 5% by mass of sodium dodecyl sulfate, carrying out oscillation treatment at a pH value of 3.0-6.0 to obtain the desorbed magnetic molecularly imprinted polymer, and washing with deionized water until the surface is free of foams to obtain the activated magnetic analysis imprinted polymer.
The embodiments of the present invention are illustrated below by specific examples, which are intended to be merely illustrative and not restrictive in any way.
Example 1
The embodiment provides a preparation method of a boric acid composite type double-template magnetic molecularly imprinted polymer, which comprises the following steps:
s1 preparation of Fe by sol-gel method 3 O 4 @SiO 2 The microsphere material:
s11, weighing 5g of Fe 3 O 4 Adding hydrochloric acid solution with concentration of 1M, soaking for 10min to activate surface hydroxyl, and washing with distilled water under external magnetic field condition for 5 times to remove hydrochloric acid interference; then activated Fe 3 O 4 Transferring into a three-neck flask containing 200mL of mixed solution of alcohol and water, performing ultrasonic treatment for 20min to uniformly disperse, and adding 5mL of NH under mechanical stirring at 400rpm 3 ·H 2 O, then diluting 6mL of ethyl orthosilicate solution into 20mL of absolute ethanol solution, and reacting for 8h at room temperature to obtain a coating; wherein, the mixed solution is ethanol and water (V/V is 4: 1);
s12, alternately washing the coating with absolute ethyl alcohol and distilled water for 3 times, then performing solid-liquid separation with a magnet, and drying the separated solid in a vacuum drying oven at 70 ℃ for 12 hours to obtain SiO 2 5 wt% -25 wt% of Fe 3 O 4 @SiO 2 A microsphere material.
S2, 2mL of 3- (methacryloyloxy) propyltrimethoxysilane was dispersed in 240mL of an aqueous solution containing 10% acetic acid, mechanically stirred at room temperature for 5 hours, and then 2g of Fe was added 3 O 4 @SiO 2 Reacting the microsphere material for 6g under the water bath condition of 60 ℃, washing a product obtained after the reaction for a plurality of times by using distilled water, separating by using a magnet to obtain a solid product, and drying in vacuum at 60 ℃ to obtain double-bond modified Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles;
s3, mixing 2g of Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles dispersed in 400mL of acetonitrileAdding 1.5g of glycidyl methacrylate, 1g of N, N-methylene bisacrylamide and 0.06g of azobisisobutyronitrile into the solution, ultrasonically dispersing for 15min, transferring the solution into a 1000mL three-neck flask, placing the three-neck flask on a magnetic stirrer, reacting in a water bath condition, connecting a fractionating column, a spherical condenser tube and a connecting tube to the mouth of the flask, washing the product obtained after the reaction with absolute ethyl alcohol for three times, separating the product with a magnet to obtain a solid product, and drying the solid product in vacuum at 45 ℃ for 24h to obtain the epoxy bond modified magnetic nano particle Fe with the core-shell structure 3 O 4 @SiO 2 -EPO; wherein the water bath temperature is set to 95 ℃, the heating time is about 35min, the boiling is started at 81.6 ℃, the mixture is collected after condensation, 200mL of acetonitrile is collected after about 60min, the heating is stopped, and the mixture is cooled to the room temperature;
s4, weighing 1.67g of 3-aminophenylboronic acid and 1.37g of 1, 6-hexanediamine serving as functional monomers, adding the functional monomers into a three-neck flask containing 240mL of absolute ethyl alcohol, stirring for 60min at 40 ℃ in a water bath, and then adding 0.5g of Fe 3 O 4 @SiO 2 Continuously reacting EPO for 12 hours under the condition of water bath at 80 ℃, repeatedly cleaning a product obtained after the reaction is finished by absolute ethyl alcohol, separating by using a magnet to obtain a solid product, and drying in vacuum at 45 ℃ to obtain the magnetic nano-particles with the combined borate affinity core-shell structure;
s5, weighing 0.5g of combined borate affinity core-shell structure magnetic nanoparticles and double-template molecules, fully dissolving in 250mL of phosphate buffer solution, performing ultrasonic treatment for 10min, oscillating for 3h at room temperature with the oscillation speed of 200rpm, adding 0.5g of dopamine and 20 mL2.5wt% of ammonium persulfate, performing polymerization reaction for 5h at room temperature, washing a product obtained after the reaction is finished for 5 times by using absolute ethyl alcohol and distilled water, washing the product for multiple times by using an eluent (5% SDS + HAc, with the pH value of 4.0) to remove template molecules until an absorption peak of BSA (bovine serum albumin) cannot be detected by using a UV-vis spectrum, washing for 5 times by using distilled water until the solution is neutral, and performing vacuum drying for 12h at 45 ℃ to obtain the boric acid composite double-template magnetic molecularly imprinted polymer; wherein the double-template molecules comprise bovine serum albumin and glucan which are 0.08g and 0.02g respectively; the phosphate buffer solution had a concentration of 0.02M and a pH of 7.4.
The embodiment also provides a boric acid composite type double-template magnetic molecularly imprinted polymer prepared by the preparation method in the embodiment.
Example 2
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 31 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 44 mg/g.
Example 3
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with initial concentration of 0.12mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 27 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1.2mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 42 mg/g.
Example 4
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.06mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 29 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 0.6mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 26 mg/g.
Example 5
The embodiment provides an application of the boric acid composite type dual-template magnetic molecularly imprinted polymer, and the boric acid composite type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing protein and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.04mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 24 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid composite type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption liquid with initial concentration of 0.4mg/mL for oscillation adsorption for 3h, separating out the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to bovine serum albumin to be 22 mg/g.
Example 6
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.02mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 18 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 0.2mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 19 mg/g.
Example 7
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with initial concentration of 0.01mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 8 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 12 mg/g.
Example 8
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 2h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 31 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 2h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 42 mg/g.
Example 9
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 1.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 26 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 1.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 38 mg/g.
Example 10
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid composite type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 1h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer on the glucan to be 22 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 1h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 24 mg/g.
Example 11
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 0.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 14 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 0.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 8.6 mg/g.
Example 12
The embodiment provides an application of a boric acid compound type dual-template magnetic molecularly imprinted polymer, wherein the boric acid compound type dual-template magnetic molecularly imprinted polymer prepared in the embodiment 1 is used as a magnetic adsorbent for adsorbing proteins and polysaccharide substances.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 3.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 30 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption solution with the initial concentration of 1mg/mL for oscillation adsorption for 3.5h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the bovine serum albumin to be 44 mg/g.
Example 13
The embodiment provides a preparation method of a boric acid composite type double-template magnetic molecularly imprinted polymer, which is different from the preparation method in embodiment 1 in that: the polymerization reaction is carried out for 2h at room temperature in step S5, and other steps and methods are the same as those in example 1 and are not repeated herein.
The embodiment also provides a boric acid composite type double-template magnetic molecularly imprinted polymer which is prepared by the preparation method in the embodiment.
Example 14
In this embodiment, an application of the boronic acid composite type dual-template magnetic molecularly imprinted polymer is provided, where the boronic acid composite type dual-template magnetic molecularly imprinted polymer prepared in example 13 is used as a magnetic adsorbent for adsorbing proteins and polysaccharides.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing protein, and specifically comprises the following steps: placing 0.01g of boric acid compound type double-template magnetic molecularly imprinted polymer in 10mL of glucan adsorption solution with the initial concentration of 0.1mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to the glucan to be 11 mg/g.
In this embodiment, the boric acid composite type dual-template magnetic molecularly imprinted polymer is used as a magnetic adsorbent for adsorbing dextran, and specifically includes: placing 0.01g of boric acid composite type dual-template magnetic molecularly imprinted polymer in 10mL of bovine serum albumin adsorption liquid with the initial concentration of 1mg/mL for oscillation adsorption for 3h, separating the magnetic molecularly imprinted polymer by a magnetic separation method, and measuring the adsorption capacity of the magnetic molecularly imprinted polymer to bovine serum albumin to be 16 mg/g.
In summary, the present invention uses magnetic inorganic particles Fe 3 O 4 Or gamma-Fe 2 O 3 As a core, Fe is formed by coating silica on the surface thereof by a sol-gel method 3 O 4 @SiO 2 Microsphere material of Fe 3 O 4 @SiO 2 The microsphere material has the advantages of low cost of raw materials, simple preparation, good water solubility, dispersibility and biocompatibility, and the surface can be modified with different functional groups through chemical modification, and the Fe is firstly modified by 3- (methacryloyloxy) propyl trimethoxy silane 3 O 4 @SiO 2 Carrying out double bond modification on the microsphere material, and modifying epoxy bonds at the double bonds by using the double bonds to obtain the epoxy bond modified magnetic nanoparticles with the core-shell structure Fe 3 O 4 @SiO 2 EPO, synthesizing a boric acid composite type double-template molecularly imprinted polymer by a boric acid affinity imprinting method and a dopamine autopolymerization imprinting technology, and specifically binding polysaccharides and proteins at the same time; in addition, the invention utilizes the characteristics of magnetic materials, adopts the magnet to separate solid from liquid, has high solid-liquid separation speed and low energy consumption, and has the advantages of easily obtained raw materials, simple and rapid method, easy separation and recycling; the boric acid compound type double-template molecularly imprinted polymer prepared by the method is used as a magnetic imprinted adsorbent, has high adsorption rate and stable adsorption performance, is easy to separate, can be repeatedly used for many times, can simultaneously adsorb two template molecules of protein and polysaccharide substances, is suitable for selectively removing membrane pollutants such as protein, polysaccharide and the like in an adsorption membrane biological reaction system, and is also suitable for selectively removing membrane pollutants such as protein, polysaccharide and the likeIn other fields, the separation, purification and enrichment of protein, polysaccharide and other types of biomacromolecules. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a boric acid composite type double-template magnetic molecularly imprinted polymer is characterized by comprising the following steps:
s1 preparation of Fe by sol-gel method 3 O 4 @SiO 2 The microsphere material:
s2, dispersing 3- (methacryloyloxy) propyltrimethoxysilane in a mixed solution of acid and water, and then adding Fe 3 O 4 @SiO 2 Reacting the microsphere material in water bath at 30-60 ℃ to obtain double bond modified Fe 3 O 4 @SiO 2 @ C ═ C magnetic particles;
s3, mixing the Fe 3 O 4 @SiO 2 Modifying double bonds on the surface of the @ C ═ C magnetic particles into epoxy bonds to obtain the epoxy bond modified magnetic nanoparticles Fe with the core-shell structure 3 O 4 @SiO 2 -EPO；
S4, in the presence of Fe 3 O 4 @SiO 2 Grafting a combined borate on an epoxy bond of EPO to obtain a combined borate affinity core-shell structure magnetic nanoparticle which is used as a magnetic carrier;
s5, weighing and fully dissolving the combined borate affinity core-shell structure magnetic nanoparticles and the double-template molecules in a buffer solution, oscillating for 1-5 h at room temperature, then adding dopamine and an initiator, and carrying out polymerization reaction for 2-8 h to obtain the boric acid composite double-template magnetic molecularly imprinted polymer.
2. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 1, characterized in that: preparation of Fe by sol-gel method described in step S1 3 O 4 @SiO 2 The method for preparing the microsphere material specifically comprises the following steps:
s11, dispersing the magnetic inorganic particles in the first alcohol solution, adding an alkaline solution under the stirring condition, then adding a second alcohol solution of tetraethoxysilane, and reacting at room temperature for 6-12 hours to obtain a coating;
s12, alternately washing the coating in the step S11 with absolute ethyl alcohol and distilled water for a plurality of times, then carrying out solid-liquid separation, drying the solid obtained by separation in a vacuum drying oven at 50-70 ℃ for 8-24 h to obtain SiO 2 5 to 25 weight percent of Fe 3 O 4 @SiO 2 A microsphere material.
3. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 2, characterized in that: step S11 includes any one or combination of the following:
in step S11, the magnetic inorganic particles are Fe 3 O 4 Or gamma-Fe 2 O 3 The size of the magnetic inorganic particles is 20 nm-30 mu m;
the first alcohol solution in step S11 includes a first alcohol and water, and the first alcohol is one or a combination of methanol, ethanol, propanol and butanol; the second glycol solution of the ethyl orthosilicate is formed by adding the ethyl orthosilicate into the second glycol solution for dilution, wherein the second glycol solution is one or a combination of methanol, ethanol, propanol and butanol; the volume ratio of the ethyl orthosilicate to the second alcohol solution is 1: 2-1: 10, the volume ratio of the ethyl orthosilicate to the first alcohol is 1: 10-1: 50, and the volume ratio of the ethyl orthosilicate to the water is 1: 1-1: 15; in the step S11, the ratio of the mass of the magnetic inorganic particles to the volume of the tetraethoxysilane is 1: 0.5-1: 15, and the volume ratio of the tetraethoxysilane to the alkaline solution is 1: 0.5-1: 10;
according to said Fe 3 O 4 @SiO 2 The mass percentage of the microsphere material is Fe 3 O 4 @SiO 2 The microsphere material comprises 0.2-12 wt% of magnetic inorganic particles, 0.3-15 wt% of ethyl orthosilicate, 2-10 wt% of alkaline solution and the balance of mixed solution of alcohol and water.
4. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 1, characterized in that: step S2 includes any one or combination of the following:
said Fe being added 3 O 4 @SiO 2 The ratio of the mass of the microsphere material to the volume of the 3- (methacryloyloxy) propyltrimethoxysilane is 1: 0.1-1: 5;
the volume ratio of the 3- (methacryloyloxy) propyl trimethoxy silane to the acid is 1: 5-1: 25;
the acid is one or a combination of acetic acid, phosphoric acid and sulfuric acid.
5. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 1, characterized by comprising the following steps: in step S3, adding Fe 3 O 4 @SiO 2 The double bond modification on the surface of the @ C ═ C magnetic particle is an epoxy bond, and specifically includes: subjecting said Fe to 3 O 4 @SiO 2 Dispersing the @ C ═ C magnetic particles in acetonitrile solution, adding glycidyl methacrylate, a crosslinking agent and azodiisobutyronitrile, and reacting in a water bath at 85-95 ℃ to obtain epoxy bond modified core-shell structure magnetic nanoparticles Fe 3 O 4 @SiO 2 -EPO。
6. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 5, characterized in that: step S3 includes any one or a combination of the following;
the glycidyl methacrylate and the Fe 3 O 4 @SiO 2 The mass ratio of the @ C ═ C magnetic particles is 1: 1-1: 5;
the crosslinking agent and the Fe 3 O 4 @SiO 2 The mass ratio of the @ C ═ C magnetic particles is 1: 1-1: 5;
the mass ratio of the azodiisobutyronitrile to the glycidyl methacrylate is 1: 20-1: 50;
the cross-linking agent is one or a combination of N, N-methylene bisacrylamide, N-1, 2-dihydroxyethylene bisacrylamide, vinyl dimethacrylate and trimethoxypropane trimethacrylate.
7. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 1, characterized in that: in step S4 in the Fe 3 O 4 @SiO 2 -grafted on the epoxy bond of EPO a combined borate, comprising in particular: adding 3-aminophenylboronic acid and 1, 6-hexamethylenediamine into a container filled with absolute ethyl alcohol, stirring for 30-90 min, and then adding the Fe 3 O 4 @SiO 2 Continuously reacting for 12 hours at the temperature of 80 ℃ in a water bath, washing the obtained product for several times by using absolute ethyl alcohol, then carrying out solid-liquid separation, and drying the separated solid to obtain the combined borate affinity core-shell structure magnetic nanoparticles;
wherein the 3-aminophenylboronic acid is reacted with the Fe 3 O 4 @SiO 2 The mass ratio of EPO is 1: 0.2-1: 2; the 1, 6-hexanediamine and the Fe 3 O 4 @SiO 2 The mass ratio of EPO to EPO is 1: 0.2-1: 2.
8. The preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer according to claim 1, characterized in that: step S5 includes any one or combination of the following:
in the step S5, the double-template molecules comprise proteins and polysaccharide substances, and the mass ratio of the proteins to the polysaccharide substances is 1: 1-1: 5;
in the step S5, the mass ratio of the double-template molecules to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 10-1: 30, the mass ratio of the dopamine to the combined borate affinity core-shell structure magnetic nanoparticles is 1: 1-1: 5, the volume ratio of the initiator to the buffer solution is 1: 10-1: 30, wherein the initiator is ammonium persulfate, and the buffer solution is phosphate buffer solution.
9. A boric acid composite type double-template magnetic molecularly imprinted polymer, which is characterized by being prepared by the preparation method of the boric acid composite type double-template magnetic molecularly imprinted polymer as described in any one of claims 1 to 8.
10. The application of the boric acid composite type double-template magnetic molecularly imprinted polymer is characterized in that: the boric acid composite type dual-template magnetic molecularly imprinted polymer as claimed in claim 9 is used as a magnetic adsorbent for adsorbing protein and polysaccharide substances.
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